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CA2115984C - The use of substantially fluorinated compounds as heat transfer agents - Google Patents

The use of substantially fluorinated compounds as heat transfer agents Download PDF

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Publication number
CA2115984C
CA2115984C CA002115984A CA2115984A CA2115984C CA 2115984 C CA2115984 C CA 2115984C CA 002115984 A CA002115984 A CA 002115984A CA 2115984 A CA2115984 A CA 2115984A CA 2115984 C CA2115984 C CA 2115984C
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Prior art keywords
fluorinated
heat transfer
transfer agent
heat
specified
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Expired - Lifetime
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CA002115984A
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French (fr)
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CA2115984A1 (en
Inventor
Wilfried Becker
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Solvay SA
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Solvay SA
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Publication of CA2115984A1 publication Critical patent/CA2115984A1/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/34Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/42Fillings or auxiliary members in containers or encapsulations selected or arranged to facilitate heating or cooling
    • H01L23/427Cooling by change of state, e.g. use of heat pipes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/102Alcohols
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/11Ethers
    • C09K2205/112Halogenated ethers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001Technical content checked by a classifier
    • H01L2924/0002Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Organic Insulating Materials (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Non-flammable, substantially fluorinated compounds from the series of alkanes and/or dialkyl ethers are suitable as heat transfer agents, in particular as coolant or insulating medium, especially for evaporative cooling.
These compounds can also be employed in a mixture with small amounts of intrinsically flammable liquids, in which case lower alkanols are preferred.

Description

HOECHST AKTIENGESELLSCHAFT HOE 93/F 906 Dr.KL-nu werk Gendorf The use of substantially fluorinated compounds as heat transfer agents Description The heat arising in components in power electronics must be removed by heat transfer agents, for example on use of power semiconductors for high voltage/direct current transmission or for railway drives. In this context it is possible for the cooling to take place by single-phase convection, that is to say without a change in the state of aggregation of the coolant, or by two-phase cooling on the principle of vaporization cooling - also called "evaporative cooling" - the two-phase cooling being considerably more efficient. In this context it is possible for the heat-generating components to lie directly in the boiling liquid, or the liquid boils in hollow cooling cells (bath or sell evaporative cooling).
Liquid halogenated hydrocarbons, especially chlorofluoro-carbons, have proven useful as heat transfer agents and, in particular, as evaporative cooling liquids. In particular, 1,1,2-Trichloro-1,2,2-trifluoroethane (F113) has been widely used as a reasonably priced evaporative cooling liquid because of its good thermal stability, non-flaam~ability, low viscosity, relatively high heat of vaporization and the favorable electrophysical and physiological properties. However, chlorofluorocarbons are regarded as damaging for the ozone in the strato-. .
sphere and must therefore be replaced by other substan-ces.
It has now been found that non-flammable, substantially fluorinated compounds from the series of alkanes with at least 3 carbon atoms and/or dialkyl ethers are suitable as heat transfer agents, in particular as coolant and insulating medium. The term "substantially fluorinated"
is in this case to be understood in connection with "non-flammable" that is to say that n~ flashpoint can be detected up to the boiling point by the DIN 51 755 method.
The choice of the fluorinated alkanes or dialkyl ethers depends on their boiling point. A suitable substitute for F113 (boiling point 47.6°C) is thus, for example, 1,4-dihydroperfluorobutane with a boiling point of 44°C, as well as higher boiling liquids such as 1-hydro-n-per-fluorohexane with a boiling point of 70°C.
Suitable examples are fluoroalkanes of the formula (1) CaF2n+a-aHa ( 1 ) in which n is 3 to 6, preferably 4 to 6, and a is . 1 to (n + 1) , as well as fluorinated ethers of the formula (2) CmFzm~i_bHb-C-CpFzp.i_oN~ ( 2 ) in which, independently of one another, m and p are 1 to 4, but (m + p) does not exceed 5, and (b + c) is 1 to (m + p + 1) .

... , ..., ... _. ., .._.,...... ....,._...,......-, .... . . . -I -..
.......,.,..._..,...",..".,_..... ,. .. "".... . ...._... , . .
....<,....,..,.__ ........

- 2a -In particular the invention provides a replacement fluid for CFC-113 which comprises a fluorinated ether of the formula:
CqFg_bHb_0-CF3_cHc wherein (b+c) is 1 to 6.
It is thus generally true that the number of hydrogen atoms at the most equals the number of fluorine atoms because the compounds with a higher hydrogen content are generally flammable.
However, the invention is not confined to pure substances but, on the contrary, also embraces mixtures of suitable liquids, which frequently have advantages simply because of easy obtainability and thus of price. However, the invention also relates to mixtures of suitable liquids which are combined for the purpose of lowering the boiling point.
It has furthermore been found that flammable liquids can also be used for suitable mixtures, for example low-fluorinated ethers which therefore contain fewer fluorine than hydrogen atoms, as long as the mixture to be employed meets the abovementioned criterion of non-flammability. Preferred mixtures are those of substan-tially fluorinated alkanes or substantially fluorinated dialkyl ethers with liquid lower dialkyl ethers, hydro-carbons and lower alkanols, especially methanol, ethanol or isopropanol, with azeotropic mixtures or mixtures with subazeotropic amounts of added liquid being preferred.
A particular advantage of lower alkanols as components of the mixture is regarded as being the fact that they react with highly fluorinated branched olefins of the octa-fluoroisobutene type (Houben-Weyl, Methoden der organischen Chemie (Methods of Organic Chemistry), 4th edition, volume V/3, page 280), which converts the usually toxic branched-chain olefins into non-toxic ethers. Said olefins may, on the one hand, be present in technical products as impurity but, on the other hand, also be formed during use as a consequence of spark discharges or other extreme stresses. This preferred embodiment of the invention thus provides additional safety during use.

- 3a -Thus, in one aspect, the present invention provides a method for removing heat from a heat-generating component, in which heat is transferred from the heat-generating component to a liquid heat transfer agent through direct contact, wherein the heat transfer agent comprises a non-flammable fluorinated alkane of formula (1) CnF2n+2-aHa ( 1 ) in which n is 3 to 6 and a is 1 to (n+1) or a non-flammable fluorinated ether of formula (2) CCmF2m+1-bHb-~-CpF2p+1-cHc (2) in which, independently of one another, m and p are 1 to 4, but (m+p) does not exceed 5, and b+c is 1 to (m+p+1), or a mixture of one of said fluorinated alkanes and one of said fluorinated ethers.
In another aspect, the present invention provides a method for removing heat from a heat-generating component, in which heat is transferred from said component to a liquid heat transfer agent through direct contact, wherein the heat transfer agent is a fluorinated compound containing at least one hydrogen atom selected from the group consisting of fluorinated alkanes with at least three carbon atoms and fluorinated dialkyl ethers.
The invention is explained in detail hereinafter by means of examples of the replacement of F113. However, it is self-evident that the scope of the invention also extends to the replacement of other halogenated hydrocarbons as heat transfer agents, in particular as coolant or insulating medium or as working medium in cooling machines such as automobile air-conditioning systems.

- 3b -Percentage data in the examples summarized in the following table mean percentages by weight. The boiling points (b.p.) are indicated in °C.

2115J8~
., Table Example~ Substance(s) I b.p.

1 i H-(CFZ)a-H (A) ' ~ 44 i ' ~ ' ~ ' 2 ~ H-(CFZ)6-H (B) ;.._70 ' ' i i ' ' ' ' ~ 3 ~ F3C-CHZ-O- ( CFZ ) z-H ~ 5 6 . 7 ( C ) ' , ' ' 4 ~ (F3C)zCF-(CFH)2-CFg ~ 68 i (D) ' ' ' i 5 ~ (F3C) ZCF-CHZ-CFH-CF3 i 65 i (E) ' ' ' ' ' , 6 ~ 17 to 7% B + 83 to 93% ~ 56 to 57*) C

' 7 ~ 21 to 11% D + 79 to + 56 to 57*) 89% C ~

' ~ ' ~ 8 ~ 96.4% A + 3.6% CH30H ~ 41.6*) r ' , , 9 ~ 92.6% B + 7.4% CH30H ~ 53.5*) ' ' , ,.
-' 10 T 90.7% B + 9.3% (CH3)zCHOH~ 63.4*) ~

' ' ' ' ., 11 ~ 93.7% C + 6.3% CZHSOH ~ 53.1*) L ' o ~ 12 i 90% E + 10% CH30H -1'49*) i i s , *) azeotropi c mixture

Claims (24)

1. A method for removing heat from a heat-generating component, in which heat is transferred from the heat-generating component to a liquid heat transfer agent through direct contact, wherein the heat transfer agent comprises a non-flammable fluorinated alkane of formula (1) C n F2n+2-a H a (1) in which n is 3 to 6 and a is 1 to (n+1) or a non-flammable fluorinated ether of formula (2) C m F2m+1-b H b-O-C p F2p+1-c H c (2) in which, independently of one another, m and p are 1 to 4, but (m+p) does not exceed 5, and b+c is 1 to (m+p+1), or a mixture of one of said fluorinated alkanes and one of said fluorinated ethers.
2. The method according to claim 1, wherein the heat transfer agent comprises: (a) one of the fluorinated alkanes specified in claim 1 or one or the fluorinated ethers specified in claim 1 or a mixture thereof and, mixed therewith, (b) a flammable lower hydrocarbon, a flammable lower alkanol or a flammable lower dialkyl ether, and wherein the heat transfer agent comprising (a) and (b) is non-flammable.
3. The method according to claim 2, wherein the heat transfer agent is an azeotropic mixture.
4. The method according to claim 1, wherein the boiling point of the fluorinated alkane specified in claim 1 and of the fluorinated ether specified in claim 1 is at a temperature of 44°C or above.
5. The method according to any one of claims 1 to 4, wherein the heat transfer agent comprises one of the fluorinated alkanes specified in claim 1.
6. The method according to claim 1, wherein the heat transfer agent consists of one of the fluorinated alkanes specified in claim 1.
7. The method according to any one of claims 1 to 4, wherein the heat transfer agent comprises one of the fluorinated ethers specified in claim 1.
8. The method according to claim 1, wherein the heat transfer agent consists of one of the fluorinated ethers specified in claim 1.
9. The method according to any one of claims 1 to 8, wherein the heat-generating component is an electronic component.
10. The method according to claim 9 for heat removal from power semiconductors for high voltage/direct current transmission.
11. The method according to claim 9, for heat removal from power semiconductors for railway drives.
12. A method for removing heat from a heat-generating component, in which heat is transferred from said component to a liquid heat transfer agent through direct contact, wherein the heat transfer agent is a fluorinated compound containing at least one hydrogen atom selected from the group consisting of fluorinated alkanes with at least three carbon atoms and fluorinated dialkyl ethers.
13. The method according to claim 12, wherein the heat transfer agent comprises: (a) one of the fluorinated alkanes specified in claim 1 or one of the fluorinated ethers specified in claim 1 or a mixture thereof and, mixed therewith, (b) a flammable lower hydrocarbon, a flammable lower alkanol or a flammable lower dialkyl ether, and wherein the heat transfer agent comprising (a) and (b) is non-flammable.
14. The method according to claim 13, wherein the heat transfer agent is an azeotropic mixture.
15. The method according to claim 12, wherein the boiling point of the fluorinated alkane and of the fluorinated ether is at a temperature of 44°C or above.
16. The method according to any one of claims 12 to 15, wherein the heat transfer agent comprises one of the fluorinated alkanes specified in claim 12.
17. The method according to claim 12, wherein the heat transfer agent consists of one of the fluorinated alkanes specified in claim 12.
18. The method according to any one of claims 12 to 15, wherein the heat transfer agent comprises one of the fluorinated ethers specified in claim 12.
19. The method according to claim 12, wherein the heat transfer agent consists of one of the fluorinated ethers specified in claim 12.
20. The method according to any one of claims 12 to 19, wherein the heat-generating component is an electronic component.
21. The method according to claim 20, for heat removal from power semiconductors for high voltage/direct current transmission.
22. The method according to claim 20, for heat removal from power semiconductors for railway drives.
23. A replacement fluid for CFC-113 which comprises a fluorinated ether of the formula:
C4F9-b H b-O-CF3-c H c wherein (b+c) is 1 to 6.
24. The fluid of claim 23, wherein the fluorinated ether is non-flammable and wherein the number of hydrogen atoms is at most equal to the number of fluorine atoms.
CA002115984A 1993-02-20 1994-02-18 The use of substantially fluorinated compounds as heat transfer agents Expired - Lifetime CA2115984C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4305239A DE4305239A1 (en) 1993-02-20 1993-02-20 Use of largely fluorinated compounds as heat transfer media
DEP4305239.8 1993-02-20

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CA2115984A1 CA2115984A1 (en) 1994-08-21
CA2115984C true CA2115984C (en) 2006-05-02

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JP (3) JPH06287550A (en)
AT (1) ATE206741T1 (en)
CA (1) CA2115984C (en)
DE (2) DE4305239A1 (en)
ES (1) ES2165369T3 (en)

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KR20060132888A (en) * 2004-01-30 2006-12-22 그레이트 레이크스 케미칼 코퍼레이션 Compositions, Halogenated Compositions, Chemical Preparations and Telomerization Methods
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JPH06287550A (en) 1994-10-11
JP2008069157A (en) 2008-03-27
DE59409901D1 (en) 2001-11-15
EP0612825A1 (en) 1994-08-31
ES2165369T3 (en) 2002-03-16
JP2005047926A (en) 2005-02-24
JP4607526B2 (en) 2011-01-05
CA2115984A1 (en) 1994-08-21
ATE206741T1 (en) 2001-10-15
DE4305239A1 (en) 1994-08-25
EP0612825B1 (en) 2001-10-10

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